Covalency is Frustrating: La2Sn2O7 and the Nature of Bonding in Pyrochlores under High Pressure–Temperature Conditions

Childs, Christian; Lawler, Keith V.; Hector, Andrew L.; Petitgirard, Sylvain; Noked, Ori; Smith, Jesse S.; Daisenberger, Dominik; Bezacier, Lucile; Jura, Marek; Pickard, Chris J.; Salamat, Ashkan

doi:10.1021/acs.inorgchem.8b01419

Title: Covalency is Frustrating: La₂Sn₂O₇ and the Nature of Bonding in Pyrochlores under High Pressure–Temperature Conditions

Journal Article · Mon Jul 02 00:00:00 EDT 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.8b01419· OSTI ID:1461560

Childs, Christian ^[1];

^[2];

^[3]; Petitgirard, Sylvain ^[4]; Noked, Ori ^[5]; Smith, Jesse S. ^[6]; Daisenberger, Dominik ^[7]; Bezacier, Lucile ^[8]; Jura, Marek ^[9]; Pickard, Chris J. ^[10]; Salamat, Ashkan ^[1]

Department of Physics and Astronomy and HiPSEC, University of Nevada Las Vegas, Las Vegas, Nevada 89154, United States
Department of Chemistry and Biochemistry and HiPSEC, University of Nevada Las Vegas, Las Vegas, Nevada 89154, United States
Department of Chemistry, University of Southampton, Southampton SO17 1BJ, United Kingdom
Bayerisches GeoInstitut (BGI), University of Bayreuth, 95444 Bayreuth, Germany
Lyman Laboratory of Physics, Harvard University, Cambridge, Massachusetts 02138, United States
High Pressure Collaborating Access Team at Advanced Photon Source, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, Illinois 60439, United States
Diamond Light Source Ltd., Didcot, Oxfordshire OX11 0DE, United Kingdom
European Synchrotron Radiation Facility, BP 220, 38043 Grenoble, Cedex 9, France
ISIS, STFC, Harwell Innovation Campus, Didcot, Oxfordshire OX11 0QX, United Kingdom
Department of Materials Science &, Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United Kingdom, Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Natural specimens of the pyrochlore (A₂B₂O₇) compounds have been found to retain foreign actinide impurities within their parent framework, undergoing metamictization to a fully amorphous state. The response to radionuclide decay identifies pyrochlore systems with having high radiation tolerance and tailored use in radioactive waste applications and radionuclide sequestration. High pressure is a powerful pathway to high density states and amorphization with parallels to radiation-induced processes. Here, La₂Sn₂O₇ is evaluated under extreme conditions via the combination of laser heating in a diamond anvil cell with X-ray diffraction and Raman spectroscopy. The measurements are supported by ab initio random structure searching and molecular dynamics calculations. A new ground state at 70 GPa is revealed, and high temperature annealing is fundamental to access its crystalline ground state and fully determine the structure. This crystalline phase (P2₁/c) retains its structural integrity during decompression and is fully recoverable to ambient conditions. The final state of the system is shown to be highly pathway dependent due to the covalent nature of the Sn-O bonding. The Tc pyrochlore, La₂Tc₂O₇, is analyzed for similarities in the bonding to determine the likelihood of an analogous pathway dependency to a final state

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Research Organization:: Univ. of Nevada, Las Vegas, NV (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); Engineering and Physical Sciences Research Council (EPSRC)

Grant/Contract Number:: NA0001982; NA0001974; FG02-99ER45775; AC02-06CH11357; EP/P022596/1

OSTI ID:: 1461560

Alternate ID(s):: OSTI ID: 1508588; OSTI ID: 1771008

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Vol. 57 Journal Issue: 24; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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Title: Covalency is Frustrating: La₂Sn₂O₇ and the Nature of Bonding in Pyrochlores under High Pressure–Temperature Conditions